JP6787309B2 - Antibacterial fiber - Google Patents

Antibacterial fiber Download PDF

Info

Publication number
JP6787309B2
JP6787309B2 JP2017506489A JP2017506489A JP6787309B2 JP 6787309 B2 JP6787309 B2 JP 6787309B2 JP 2017506489 A JP2017506489 A JP 2017506489A JP 2017506489 A JP2017506489 A JP 2017506489A JP 6787309 B2 JP6787309 B2 JP 6787309B2
Authority
JP
Japan
Prior art keywords
fiber
polyacetal copolymer
antibacterial
group
polyacetal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
JP2017506489A
Other languages
Japanese (ja)
Other versions
JPWO2016147998A1 (en
Inventor
顕 伊東
顕 伊東
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Publication of JPWO2016147998A1 publication Critical patent/JPWO2016147998A1/en
Application granted granted Critical
Publication of JP6787309B2 publication Critical patent/JP6787309B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
    • B01D39/083—Filter cloth, i.e. woven, knitted or interlaced material of organic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/04—Copolyoxymethylenes
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
    • B01D39/1615—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of natural origin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
    • B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
    • B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
    • B01D39/163—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin sintered or bonded
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2003—Glass or glassy material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2003—Glass or glassy material
    • B01D39/2017—Glass or glassy material the material being filamentary or fibrous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2055—Carbonaceous material
    • B01D39/2065—Carbonaceous material the material being fibrous
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/18—Copolymerisation of aldehydes or ketones
    • C08G2/24—Copolymerisation of aldehydes or ketones with acetals
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • D01D5/0985—Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/66—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyethers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
    • D04B1/16—Other fabrics or articles characterised primarily by the use of particular thread materials synthetic threads
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B1/00—Shirts
    • A41B1/08—Details
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B11/00—Hosiery; Panti-hose
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B11/00—Hosiery; Panti-hose
    • A41B11/14—Panti-hose; Body-stockings
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B15/00—Handkerchiefs
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B17/00—Selection of special materials for underwear
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B2400/00—Functions or special features of shirts, underwear, baby linen or handkerchiefs not provided for in other groups of this subclass
    • A41B2400/34—Functions or special features of shirts, underwear, baby linen or handkerchiefs not provided for in other groups of this subclass antimicrobial or antibacterial
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B2500/00—Materials for shirts, underwear, baby linen or handkerchiefs not provided for in other groups of this subclass
    • A41B2500/10—Knitted
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B2500/00—Materials for shirts, underwear, baby linen or handkerchiefs not provided for in other groups of this subclass
    • A41B2500/20—Woven
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B2500/00—Materials for shirts, underwear, baby linen or handkerchiefs not provided for in other groups of this subclass
    • A41B2500/30—Non-woven
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
    • A41D13/04—Aprons; Fastening devices for aprons
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D23/00—Scarves; Head-scarves; Neckerchiefs
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D25/00—Neckties
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D2600/00—Uses of garments specially adapted for specific purposes
    • A41D2600/10—Uses of garments specially adapted for specific purposes for sport activities
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/30—Antimicrobial, e.g. antibacterial
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G9/00—Bed-covers; Counterpanes; Travelling rugs; Sleeping rugs; Sleeping bags; Pillows
    • A47G9/02—Bed linen; Blankets; Counterpanes
    • A47G9/0238—Bed linen
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
    • A63H3/00—Dolls
    • A63H3/02—Dolls made of fabrics or stuffed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
    • B01D2239/0216—Bicomponent or multicomponent fibres
    • B01D2239/0233—Island-in-sea
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0407—Additives and treatments of the filtering material comprising particulate additives, e.g. adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0442—Antimicrobial, antibacterial, antifungal additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0457—Specific fire retardant or heat resistant properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0471—Surface coating material
    • B01D2239/0492—Surface coating material on fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/0604—Arrangement of the fibres in the filtering material
    • B01D2239/0622—Melt-blown
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/0604—Arrangement of the fibres in the filtering material
    • B01D2239/0627—Spun-bonded
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/18—Copolymerisation of aldehydes or ketones
    • C08G2/22—Copolymerisation of aldehydes or ketones with epoxy compounds
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/06—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/06—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyethers
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/13—Physical properties anti-allergenic or anti-bacterial
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/02—Underwear
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/02—Underwear
    • D10B2501/021—Hosiery; Panti-hose
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/04—Outerwear; Protective garments
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/04—Outerwear; Protective garments
    • D10B2501/041—Gloves
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/04—Outerwear; Protective garments
    • D10B2501/042—Headwear
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/04—Outerwear; Protective garments
    • D10B2501/045—Neckties
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2503/00—Domestic or personal
    • D10B2503/02—Curtains
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2503/00—Domestic or personal
    • D10B2503/04—Floor or wall coverings; Carpets
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2503/00—Domestic or personal
    • D10B2503/06—Bed linen
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/04—Filters

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Filtering Materials (AREA)
  • Nonwoven Fabrics (AREA)
  • Woven Fabrics (AREA)
  • Knitting Of Fabric (AREA)
  • Multicomponent Fibers (AREA)

Description

本発明は、ポリアセタールコポリマーを表面に有する抗菌用繊維に関する。また、前記抗菌用繊維を用いた不織布、編物、織物、フェルト、及びウェブに関する。更には、前記不織布を用いたフィルター、前記した編物、織物、フェルト、及びウェブからなる群より選択されるいずれか１種以上を用いた衣料、寝具又はインテリア具に関する。 The present invention relates to antibacterial fibers having a polyacetal copolymer on the surface. The present invention also relates to non-woven fabrics, knitted fabrics, woven fabrics, felts, and webs using the antibacterial fibers. Furthermore, the present invention relates to clothing, bedding or interior equipment using any one or more selected from the group consisting of the filter using the non-woven fabric, the knitted fabric, the woven fabric, the felt, and the web.

ポリアセタールは、機械的物性、耐熱性、耐薬品性、電気的特性に優れたエンジニアリングプラスチックであり、電機、自動車、機械、建材などの分野で幅広く利用されている。また、成形加工も容易なため、繊維、不織布、フィルターとしても利用されている（例えば、特許文献１〜３を参照）。 Polyacetal is an engineering plastic having excellent mechanical properties, heat resistance, chemical resistance, and electrical properties, and is widely used in fields such as electric appliances, automobiles, machines, and building materials. Further, since it is easy to mold, it is also used as a fiber, a non-woven fabric, and a filter (see, for example, Patent Documents 1 to 3).

一方、社会の発展に伴って、プラスチックには上記した物性のほかに細菌への耐性（抗菌性）が要求されてきている。しかし、プラスチックは、誘電材料ないし電気絶縁材料としての性質を有しているため空気中の塵埃や細菌を吸着しやすく、温度及び湿度の条件が揃うと、その表面に細菌が増殖しやすい性質がある。細菌の増殖は、外観の悪化、悪臭の発生原因となり、また接触したものの汚染原因ともなる。例えば、モラクセラ菌は、洗濯後の衣類に発生する雑巾様臭を有する４−メチル−３−ヘキセン酸の発生原因として知られている。 On the other hand, with the development of society, plastics are required to have resistance to bacteria (antibacterial property) in addition to the above-mentioned physical properties. However, since plastic has properties as a dielectric material or an electrically insulating material, it easily adsorbs dust and bacteria in the air, and when the temperature and humidity conditions are met, the property is that bacteria easily grow on the surface. is there. Bacterial growth causes deterioration of appearance, generation of foul odors, and contamination of contacted materials. For example, Moraxella is known to be the cause of 4-methyl-3-hexenoic acid, which has a rag-like odor that occurs in clothes after washing.

プラスチックの抗菌性を改善する手法としては、２−（４−チアゾリル）−ベンゾイミダゾール（チアベンダゾール）などの有機系抗菌剤、又は銀、銅、亜鉛イオンなどの金属イオンを含有する物質などの無機系抗菌剤をプラスチックへ練りこむ方法、あるいは前記した有機系抗菌剤、又は無機系抗菌剤をプラスチック成形体の表面へコーティングする方法が知られている（例えば、特許文献４、５を参照）。 As a method for improving the antibacterial property of plastics, organic antibacterial agents such as 2- (4-thiazolyl) -benzimidazole (thiabendazole) or inorganic substances such as substances containing metal ions such as silver, copper and zinc ions are used. A method of kneading an antibacterial agent into a plastic, or a method of coating the above-mentioned organic antibacterial agent or an inorganic antibacterial agent on the surface of a plastic molded body is known (see, for example, Patent Documents 4 and 5).

ポリアセタールに対しても抗菌性を改善する方法が提案されている。例えば、特許文献４は、ポリアセタールに安息香酸亜鉛、硫酸亜鉛、酸化亜鉛などの金属イオンを含有する物質を溶融混練した樹脂組成物を開示している。また、特許文献５は、ポリアセタールにポリ−β−アラニン重合体と無機系抗菌剤ゼオライトを溶融混練した樹脂組成物を開示している。更に、特許文献６は、ポリアセタールにコハク酸ジメチル・１−（２−ヒドロキシエチル）−４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン重縮合物などの特定のヒンダードアミン系物質を溶融混練した樹脂組成物を開示している。 A method for improving antibacterial properties against polyacetal has also been proposed. For example, Patent Document 4 discloses a resin composition in which a substance containing metal ions such as zinc benzoate, zinc sulfate, and zinc oxide is melt-kneaded with polyacetal. Further, Patent Document 5 discloses a resin composition obtained by melt-kneading a poly-β-alanine polymer and an inorganic antibacterial agent zeolite into polyacetal. Further, Patent Document 6 melts and kneads a specific hindered amine substance such as dimethyl 1- (2-hydroxyethyl) succinate-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate in polyacetal. The resin composition is disclosed.

特開２００８−１６３５０５号公報JP-A-2008-163505 特開２００４−３６０１４６号公報Japanese Unexamined Patent Publication No. 2004-360146 特開２００５−１３８２９号公報Japanese Unexamined Patent Publication No. 2005-13829 特開平５−２３０３２５号公報Japanese Unexamined Patent Publication No. 5-230325 特開平９−２９１１９３号公報Japanese Unexamined Patent Publication No. 9-291193 特開平１０−２６５５８５号公報Japanese Unexamined Patent Publication No. 10-265585

しかし、有機系抗菌剤は、外観、耐熱性、安全性（例えば、発がん性やアトピー性）、樹脂親和性などの点で課題を有する場合が多い。例えば、前記チアベンダゾールは、プラスチックと混合しても非常にブリードしやすいため、持続的な抗菌効果（抗菌性）は期待できない。また、ブリードによって成形品表面が白く粉をふいた状態になったり、成形品表面がべとついたりする等の問題があることが知られている。更に、安全性の面でも発ガン性があることが知られている。また、有機系抗菌剤はプラスチック材料と溶融混練する際に熱で分解しやすいという課題も有する（例えば、特許文献４を参照）。 However, organic antibacterial agents often have problems in terms of appearance, heat resistance, safety (for example, carcinogenicity and atopy), resin affinity, and the like. For example, the tiabendazole is very easy to bleed even when mixed with a plastic, so that a long-lasting antibacterial effect (antibacterial property) cannot be expected. Further, it is known that there are problems such as the surface of the molded product becoming white and dusted due to bleeding, and the surface of the molded product becoming sticky. Furthermore, it is known to be carcinogenic in terms of safety. Further, the organic antibacterial agent also has a problem that it is easily decomposed by heat when melt-kneaded with a plastic material (see, for example, Patent Document 4).

一方、無機系抗菌剤を用いる場合、抗菌効果を付与するためにはプラスチックへの多量の添加（例えば１〜２重量％）が必要である、摩擦などによるプラスチックから脱落が起こるため持続的な効果に劣る、水や溶剤との接触によって溶出するなどの課題がある。 On the other hand, when an inorganic antibacterial agent is used, a large amount of addition to the plastic (for example, 1 to 2% by weight) is required to impart the antibacterial effect, and the plastic falls off due to friction or the like, so that the effect is sustained. There are problems such as inferiority and elution by contact with water or solvent.

本発明は、優れた抗菌性を有し、洗濯を繰り返しても抗菌性が持続する、抗菌用繊維を提供することを目的とする。また、前記抗菌用繊維を用いた、抗菌性に優れる不織布、編物、織物、フェルト、及びウェブを提供することを目的とする。更には、前記不織布を用いたフィルター、前記した編物、織物、フェルト、及びウェブからなる群より選択されるいずれか１種以上を用いた衣料、寝具又はインテリア具を提供することを目的とする。 An object of the present invention is to provide an antibacterial fiber having excellent antibacterial properties and maintaining antibacterial properties even after repeated washing. Another object of the present invention is to provide a non-woven fabric, knitted fabric, woven fabric, felt, and web having excellent antibacterial properties using the antibacterial fiber. Furthermore, it is an object of the present invention to provide clothing, bedding or interior equipment using any one or more selected from the group consisting of the filter using the non-woven fabric, the knitted fabric, the woven fabric, the felt, and the web.

本発明者は、上記課題について鋭意検討した結果、特定量のオキシアルキレン基を含むポリアセタールコポリマーを表面に有する繊維が、優れた抗菌性を有し、洗濯を繰り返しても抗菌性が持続することを見出し、本発明を完成するに至った。 As a result of diligent studies on the above problems, the present inventor has found that fibers having a polyacetal copolymer containing a specific amount of oxyalkylene group on the surface have excellent antibacterial properties, and the antibacterial properties are maintained even after repeated washing. We have found and completed the present invention.

即ち、本発明は、以下である。
（１）オキシメチレン基と下記一般式（１）で表されるオキシアルキレン基を有するポリアセタールコポリマー（Ｘ）を表面に有する繊維であって、ポリアセタールコポリマー（Ｘ）中のオキシアルキレン基のモル量が、オキシメチレン基のモル量とオキシアルキレン基のモル量の合計値に対して０．２〜５ｍｏｌ％である、抗菌用繊維。

（式中、Ｒ０及びＲ０’は、同一又は異なってもよく、それぞれ、水素原子、炭素数１〜８のアルキル基、炭素数１〜８のアルキル基を有する有機基、フェニル基、及びフェニル基を有する有機基から選択され、ｍは、２〜６の整数である。）
（２）前記ポリアセタールコポリマー（Ｘ）の配向度が６０％以上である、（１）に記載の抗菌用繊維。
（３）前記ポリアセタールコポリマー（Ｘ）を表面に有する繊維が、ポリアセタールコポリマー（Ｘ）の単層繊維である、（１）又は（２）に記載の抗菌用繊維。
（４）前記ポリアセタールコポリマー（Ｘ）を表面に有する繊維が、熱可塑性樹脂からなる繊維をポリアセタールコポリマー（Ｘ）で被覆した多層繊維である、（１）又は（２）に記載の抗菌用繊維。
（５）前記ポリアセタールコポリマー（Ｘ）を表面に有する繊維が、熱可塑性樹脂からなる繊維の表面にポリアセタールコポリマー（Ｘ）を有する複合繊維である、（１）又は（２）に記載の抗菌用繊維。
（６）前記熱可塑性樹脂が、ポリアセタールホモポリマー、ポリアセタールコポリマー（Ｘ）以外のポリアセタールコポリマー、ポリオレフィン樹脂、ポリ乳酸樹脂、ナイロン樹脂、ポリエステル樹脂、ポリビニル樹脂、及びこれらのエラストマーから選択される１種類又は２種類以上である、（４）又は（５）に記載の抗菌用繊維。
（７）（１）〜（６）のいずれか一項に記載の抗菌用繊維を用いた不織布。
（８）（７）に記載の不織布を用いたフィルター。
（９）（１）〜（６）のいずれか一項に記載の抗菌用繊維を用いた編物。
（１０）（１）〜（６）のいずれか一項に記載の抗菌用繊維を用いた織物。
（１１）（１）〜（６）のいずれか一項に記載の抗菌用繊維を用いたフェルト。
（１２）（１）〜（６）のいずれか一項に記載の抗菌用繊維を用いたウェブ。
（１３）（９）〜（１２）に記載の編物、織物、フェルト、及びウェブからなる群より選択されるいずれか１種以上を用いた衣料。
（１４）（９）〜（１２）に記載の編物、織物、フェルト、及びウェブからなる群より選択されるいずれか１種以上を用いた寝具。
（１５）（９）〜（１２）に記載の編物、織物、フェルト、及びウェブからなる群より選択されるいずれか１種以上を用いたインテリア具。That is, the present invention is as follows.
(1) A fiber having a polyacetal copolymer (X) having an oxymethylene group and an oxyalkylene group represented by the following general formula (1) on its surface, and the molar amount of the oxyalkylene group in the polyacetal copolymer (X) is , 0.2 to 5 mol% with respect to the total amount of the molar amount of the oxymethylene group and the molar amount of the oxyalkylene group.

(In the formula, R 0 and R 0'may be the same or different, respectively, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an organic group having an alkyl group having 1 to 8 carbon atoms, a phenyl group, and a phenyl group, respectively. Selected from organic groups with phenyl groups, m is an integer of 2-6.)
(2) The antibacterial fiber according to (1), wherein the polyacetal copolymer (X) has an orientation degree of 60% or more.
(3) The antibacterial fiber according to (1) or (2), wherein the fiber having the polyacetal copolymer (X) on its surface is a single-layer fiber of the polyacetal copolymer (X).
(4) The antibacterial fiber according to (1) or (2), wherein the fiber having the polyacetal copolymer (X) on its surface is a multilayer fiber in which a fiber made of a thermoplastic resin is coated with the polyacetal copolymer (X).
(5) The antibacterial fiber according to (1) or (2), wherein the fiber having the polyacetal copolymer (X) on the surface is a composite fiber having the polyacetal copolymer (X) on the surface of the fiber made of a thermoplastic resin. ..
(6) The thermoplastic resin is selected from a polyacetal homopolymer, a polyacetal copolymer other than the polyacetal copolymer (X), a polyolefin resin, a polylactic acid resin, a nylon resin, a polyester resin, a polyvinyl resin, and an elastomer thereof. The antibacterial fiber according to (4) or (5), which is two or more types.
(7) A non-woven fabric using the antibacterial fiber according to any one of (1) to (6).
(8) A filter using the non-woven fabric according to (7).
(9) A knitted fabric using the antibacterial fiber according to any one of (1) to (6).
(10) A woven fabric using the antibacterial fiber according to any one of (1) to (6).
(11) A felt using the antibacterial fiber according to any one of (1) to (6).
(12) A web using the antibacterial fiber according to any one of (1) to (6).
(13) Clothing using any one or more selected from the group consisting of knitted fabrics, woven fabrics, felts, and webs according to (9) to (12).
(14) Bedding using any one or more selected from the group consisting of knitted fabrics, woven fabrics, felts, and webs according to (9) to (12).
(15) An interior tool using any one or more selected from the group consisting of knitted fabrics, woven fabrics, felts, and webs according to (9) to (12).

本発明によれば、優れた抗菌性を有し、洗濯を繰り返しても抗菌性が持続する、抗菌用繊維を提供できる。また、本発明の抗菌用繊維は、抗菌性に優れた不織布、編物、織物、フェルト、及びウェブに加工でき、これらを用いた抗菌性に優れたフィルター、衣料、寝具、及びインテリア具を提供できる。 According to the present invention, it is possible to provide an antibacterial fiber having excellent antibacterial properties and maintaining antibacterial properties even after repeated washing. In addition, the antibacterial fiber of the present invention can be processed into non-woven fabrics, knitted fabrics, woven fabrics, felts, and webs having excellent antibacterial properties, and filters, clothing, bedding, and interior tools having excellent antibacterial properties can be provided using these. ..

＜抗菌用繊維＞
以下、本発明について詳細に説明する。本発明は、オキシメチレン基と後述する一般式（１）で表されるオキシアルキレン基を有するポリアセタールコポリマー（Ｘ）を表面に有する繊維であって、ポリアセタールコポリマー（Ｘ）中のオキシアルキレン基のモル量が、オキシメチレン基のモル量とオキシアルキレン基のモル量の合計値に対して０．２〜５ｍｏｌ％である、抗菌用繊維である。すなわち、本発明の抗菌用繊維は、後述する一般式（１）で表されるオキシアルキレン基を、オキシメチレン基のモル量とオキシアルキレン基のモル量の合計値に対して０．２〜５ｍｏｌ％有するポリアセタールコポリマー（Ｘ）を、繊維の表面に有することを特徴とする。<Antibacterial fiber>
Hereinafter, the present invention will be described in detail. The present invention is a fiber having a polyacetal copolymer (X) having an oxymethylene group and an oxyalkylene group represented by the general formula (1) described later on the surface, and the molar of the oxyalkylene group in the polyacetal copolymer (X). The amount is 0.2 to 5 mol% with respect to the total amount of the molar amount of the oxymethylene group and the molar amount of the oxyalkylene group, which is an antibacterial fiber. That is, in the antibacterial fiber of the present invention, the oxyalkylene group represented by the general formula (1) described later is 0.2 to 5 mol with respect to the total value of the molar amount of the oxymethylene group and the molar amount of the oxyalkylene group. It is characterized by having a polyacetal copolymer (X) having% on the surface of the fiber.

本発明の抗菌用繊維は、前記ポリアセタールコポリマー（Ｘ）を表面に有する繊維である。ポリアセタールコポリマー（Ｘ）を表面に有する繊維の形態は特に限定されないが、好ましくは、［Ａ］ポリアセタールコポリマー（Ｘ）の単層繊維の形態、［Ｂ］熱可塑性樹脂からなる繊維をポリアセタールコポリマー（Ｘ）で被覆した多層繊維の形態、［Ｃ］熱可塑性樹脂からなる繊維の表面にポリアセタールコポリマー（Ｘ）を有する複合繊維、の形態である。 The antibacterial fiber of the present invention is a fiber having the polyacetal copolymer (X) on its surface. The form of the fiber having the polyacetal copolymer (X) on the surface is not particularly limited, but preferably, the form of the single-layer fiber of the [A] polyacetal copolymer (X) and the fiber composed of the [B] thermoplastic resin are used as the polyacetal copolymer (X). ), And a composite fiber having a polyacetal copolymer (X) on the surface of the fiber made of [C] thermoplastic resin.

上述した［Ａ］ポリアセタールコポリマー（Ｘ）の単層繊維の形態は、ポリアセタールコポリマー（Ｘ）からなる繊維である。単層繊維は、ポリアセタールコポリマー（Ｘ）を溶融紡糸して得られ、必要に応じてさらに延伸加工して得ることができる。 The monolayer fiber form of the above-mentioned [A] polyacetal copolymer (X) is a fiber composed of the polyacetal copolymer (X). The monolayer fiber is obtained by melt-spinning the polyacetal copolymer (X), and can be further stretched if necessary.

上述した［Ｂ］表面がポリアセタールコポリマー（Ｘ）で被覆された多層繊維の形態における芯部分としては、熱可塑性樹脂からなる繊維を使用することができる。前記熱可塑性樹脂の種類は特に限定されないが、例えば、ポリアセタールホモポリマー、ポリアセタールコポリマー（Ｘ）以外のポリアセタールコポリマー（例えば、一般式（１）で表されるオキシアルキレン基の含有量が、オキシメチレン基のモル量とオキシアルキレン基のモル量の合計値に対して５ｍｏｌ％を超えるポリアセタールコポリマー）、ポリオレフィン樹脂、ポリ乳酸樹脂、ナイロン樹脂、ポリエステル樹脂、ポリビニル樹脂、及びこれらのエラストマーなどが挙げられる。これらの熱可塑性樹脂は、１種類を単独であるいは２種類以上を積層または相溶させて使用できる。なお、本発明でいう「被覆」とは、芯繊維の繊維方向に対して平行な表面の全部または一部が覆われた形態をいう。表面の被覆の割合は特に限定されるものではないが、割合が高いほど抗菌性に優れるため好ましい。 As the core portion in the form of the multilayer fiber whose surface [B] is coated with the polyacetal copolymer (X) described above, a fiber made of a thermoplastic resin can be used. The type of the thermoplastic resin is not particularly limited, but for example, a polyacetal copolymer other than the polyacetal homopolymer and the polyacetal copolymer (X) (for example, the content of the oxyalkylene group represented by the general formula (1) is an oxymethylene group. Polyacetal copolymer (polyacetal copolymer exceeding 5 mol%), polyolefin resin, polylactic acid resin, nylon resin, polyester resin, polyvinyl resin, and elastomers thereof, etc., based on the total value of the molar amount of oxyalkylene group and the molar amount of oxyalkylene group. These thermoplastic resins can be used alone or in combination of two or more. The term "coating" as used in the present invention refers to a form in which all or part of a surface parallel to the fiber direction of the core fiber is covered. The proportion of the surface coating is not particularly limited, but the higher the proportion, the better the antibacterial property, which is preferable.

このような多層繊維は、ポリアセタールコポリマー（Ｘ）と上述の熱可塑性樹脂を溶融紡糸して得られ、必要に応じてさらに延伸加工して得ることができる。得られた多層繊維の形態は、芯繊維である熱可塑性樹脂からなる繊維のまわりの全部または一部を、ポリアセタールコポリマー（Ｘ）が被覆する芯鞘構造となる。 Such a multilayer fiber is obtained by melt-spinning a polyacetal copolymer (X) and the above-mentioned thermoplastic resin, and can be further stretched if necessary. The form of the obtained multilayer fiber has a core-sheath structure in which the polyacetal copolymer (X) covers all or a part of the fiber made of the thermoplastic resin which is the core fiber.

上述した［Ｃ］熱可塑性樹脂からなる繊維の表面にポリアセタールコポリマー（Ｘ）を有する複合繊維の形態における熱可塑性樹脂の種類は特に限定されず、上述した多層繊維の形態における熱可塑性樹脂と同じものを使用することができる。これらの熱可塑性樹脂は、１種類を単独であるいは２種類以上を積層または相溶させて使用できる。 The type of the thermoplastic resin in the form of the composite fiber having the polyacetal copolymer (X) on the surface of the fiber made of the above-mentioned [C] thermoplastic resin is not particularly limited, and is the same as the thermoplastic resin in the form of the above-mentioned multilayer fiber. Can be used. These thermoplastic resins can be used alone or in combination of two or more.

熱可塑性樹脂からなる繊維の表面にポリアセタールコポリマー（Ｘ）を有する複合繊維は、ポリアセタールコポリマー（Ｘ）と上述の熱可塑性樹脂の混合物を溶融紡糸して得られ、必要に応じてさらに延伸加工して得ることができる。得られた複合繊維の形態は、ポリアセタールコポリマー（Ｘ）が熱可塑性樹脂と相溶した状態となってポリマー分子レベルで繊維表面に露出している状態であってよく、海島構造またはそれに由来した分散状態となって繊維表面にポリアセタールコポリマー（Ｘ）が露出している状態であってよく、サイドバイサイドのようにポリアセタールコポリマー（Ｘ）と熱可塑性樹脂が表面に露出している状態であってもよい。前記複合繊維表面におけるポリアセタールコポリマー（Ｘ）の露出割合は特に限定されるものではないが、割合が高いほど抗菌性に優れるため好ましい。 A composite fiber having a polyacetal copolymer (X) on the surface of a fiber made of a thermoplastic resin is obtained by melt-spinning a mixture of the polyacetal copolymer (X) and the above-mentioned thermoplastic resin, and further drawing processing if necessary. Obtainable. The form of the obtained composite fiber may be a state in which the polyacetal copolymer (X) is in a state of being compatible with a thermoplastic resin and exposed on the fiber surface at the polymer molecular level, and is a sea-island structure or a dispersion derived from the sea-island structure. In this state, the polyacetal copolymer (X) may be exposed on the fiber surface, or the polyacetal copolymer (X) and the thermoplastic resin may be exposed on the surface as in the side-by-side manner. The exposure ratio of the polyacetal copolymer (X) on the surface of the composite fiber is not particularly limited, but the higher the ratio, the better the antibacterial property, which is preferable.

本発明の抗菌用繊維におけるポリアセタールコポリマー（Ｘ）の配向度は特に限定されないが、６０％以上が好ましく、７０％以上がより好ましく、８０％以上が特に好ましい。これは、ポリアセタールコポリマー（Ｘ）の配向度が高いほど抗菌性に優れるからである。また、後述するようにポリアセタールコポリマー（Ｘ）の抗菌性は、コポリマーのオキシアルキレン基含有量と相関があり、オキシアルキレン基含有量が多いポリアセタールコポリマー（Ｘ）は抗菌性が低くなる傾向がある。しかし、オキシアルキレン基含有量が多いポリアセタールコポリマー（Ｘ）ほど、抗菌性に対する配向度の影響が大きい特徴があるので、オキシアルキレン基含有量が多いポリアセタールコポリマー（Ｘ）においては、配向度が高いほど抗菌性に優れる。ポリアセタールコポリマー（Ｘ）の配向度は、溶融紡糸した繊維を延伸加工することで、効率よく高くできる。 The degree of orientation of the polyacetal copolymer (X) in the antibacterial fiber of the present invention is not particularly limited, but is preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more. This is because the higher the degree of orientation of the polyacetal copolymer (X), the better the antibacterial property. Further, as will be described later, the antibacterial property of the polyacetal copolymer (X) has a correlation with the oxyalkylene group content of the copolymer, and the polyacetal copolymer (X) having a large oxyalkylene group content tends to have a low antibacterial property. However, the polyacetal copolymer (X) having a higher oxyalkylene group content has a characteristic that the degree of orientation has a greater effect on the antibacterial property. Therefore, in the polyacetal copolymer (X) having a higher oxyalkylene group content, the higher the degree of orientation. Has excellent antibacterial properties. The degree of orientation of the polyacetal copolymer (X) can be efficiently increased by drawing the melt-spun fibers.

抗菌用繊維の配向度は、本明細書の実施例で述べるように広角Ｘ線回折装置を用いて求めることができる。 The degree of orientation of the antibacterial fiber can be determined by using a wide-angle X-ray diffractometer as described in the examples of the present specification.

本発明の抗菌用繊維の単繊度は、用途に応じて許容値が異なるため特に限定されないが、フィルターとして用いる場合は流体に対する圧力損失を小さくしながらろ過精度を高める必要があるので、１０ｄｔｅｘ（単位：デシテックス）以下であることが好ましい。 The single fiber degree of the antibacterial fiber of the present invention is not particularly limited because the permissible value differs depending on the application, but when used as a filter, it is necessary to improve the filtration accuracy while reducing the pressure loss on the fluid, so 10 dtex (unit). : Decitex) It is preferable that it is less than or equal to.

本発明の抗菌用繊維は、ＪＩＳ Ｌ １９０２（繊維製品の抗菌性試験方法及び抗菌効果）に準拠した抗菌性試験で得られる静菌活性値が、食中毒の原因菌として知られる黄色ブドウ球菌の場合、通常２．２以上であり、好ましくは２．４以上であり、特に好ましくは２．７以上である。この数値は、一般社団法人 繊維評価技術協議会で定める抗菌防臭加工の認証を満足するものである。また、本発明の抗菌用繊維は、黄色ブドウ球菌の殺菌活性値も優れる特徴がある。更にポリアセタール繊維中に抗菌性物質を練りこんで得られる抗菌用繊維に比べて、洗濯を繰り返しても抗菌性が持続するという優れた特徴がある。 The antibacterial fiber of the present invention has a bacteriostatic activity value obtained in an antibacterial test based on JIS L 1902 (antibacterial test method and antibacterial effect of textile products) when Staphylococcus aureus is known as a causative bacterium of food poisoning. , Usually 2.2 or more, preferably 2.4 or more, and particularly preferably 2.7 or more. This value satisfies the certification of antibacterial and deodorant processing specified by the Japan Textile Evaluation Technology Council. In addition, the antibacterial fiber of the present invention is characterized by having an excellent bactericidal activity value of Staphylococcus aureus. Further, as compared with the antibacterial fiber obtained by kneading an antibacterial substance into the polyacetal fiber, it has an excellent feature that the antibacterial property is maintained even after repeated washing.

本発明の抗菌用繊維は、悪臭の原因となるモラクセラ菌においても高い静菌活性値を示す。モラクセラ菌における静菌活性値は、通常１．８以上であり、好ましくは２．０以上であり、特に好ましくは、２．２以上である。また、本発明の抗菌用繊維は、モラクセラ菌に対しても優れた殺菌活性値を示す特徴がある。更にポリアセタール繊維中に抗菌性物質を練りこんで得られる抗菌用繊維に比べて洗濯を繰り返しても抗菌性が持続するという優れた特徴がある。 The antibacterial fiber of the present invention also exhibits a high bacteriostatic activity value in Moraxella, which causes malodor. The bacteriostatic activity value in Moraxella is usually 1.8 or more, preferably 2.0 or more, and particularly preferably 2.2 or more. In addition, the antibacterial fiber of the present invention is characterized by exhibiting an excellent bactericidal activity value against Moraxella. Further, it has an excellent feature that the antibacterial property is maintained even after repeated washing as compared with the antibacterial fiber obtained by kneading an antibacterial substance into the polyacetal fiber.

＜抗菌用繊維の製造方法＞
本発明の抗菌用繊維は、従来公知の繊維の製造方法にしたがって製造できる。例えば、例えば、ポリアセタールコポリマー（Ｘ）のペレットを溶融紡糸して製造できる。その際、上述した配向度を高くできる点から、溶融紡糸した繊維を更に延伸加工するのが好ましい。延伸加工の条件も従来公知の方法、条件で行うことができる。延伸倍率は、配向度の観点から３倍以上であるのが好ましい。延伸倍率の上限は配向度の点で限定されるものではないが、生産時の安定性（糸切れ防止）や過度なフィブリル化防止の点から１５倍である。なお、溶融紡糸、延伸加工の装置は、従来公知の装置を用いて行うことができる。<Manufacturing method of antibacterial fiber>
The antibacterial fiber of the present invention can be produced according to a conventionally known method for producing a fiber. For example, it can be produced by melt spinning pellets of a polyacetal copolymer (X), for example. At that time, it is preferable to further draw the melt-spun fiber from the viewpoint of increasing the degree of orientation described above. The stretching process can also be performed by conventionally known methods and conditions. The draw ratio is preferably 3 times or more from the viewpoint of the degree of orientation. The upper limit of the draw ratio is not limited in terms of the degree of orientation, but is 15 times in terms of stability during production (prevention of yarn breakage) and prevention of excessive fibrillation. The apparatus for melt spinning and drawing can be performed using a conventionally known apparatus.

＜ポリアセタールコポリマー（Ｘ）＞
本発明の抗菌用繊維の表面に存在するポリアセタールコポリマー（Ｘ）は、分子中にオキシメチレン基（−ＣＨ２−Ｏ−）以外に、下記一般式（１）で表される構造のオキシアルキレン基を有する。

式中、Ｒ０及びＲ０’は、同一又は異なってもよく、それぞれ、水素原子、炭素数１〜８のアルキル基、炭素数１〜８のアルキル基を有する有機基、フェニル基、及びフェニル基を有する有機基から選択される。また、ｍは、２〜６の整数である。好ましくは、Ｒ０及びＲ０’は、同一又は異なってもよく、それぞれ、水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、フェニル基及びベンジル基から選択され、ｍは、２〜４の整数である。より好ましくは、Ｒ０及びＲ０’は、水素原子及び炭素数１〜４のアルキル基から選択され、ｍは、２である。<Polyacetal copolymer (X)>
Polyacetal copolymer present on the surface of the antimicrobial fiber of the present invention (X), in addition to oxymethylene groups (-CH 2 -O-) in the molecule, the oxyalkylene groups of the structure represented by the following general formula (1) Has.

In the formula, R 0 and R 0'may be the same or different, respectively, an organic group having a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a phenyl group, and a phenyl group. Selected from organic groups with groups. Further, m is an integer of 2 to 6. Preferably, R 0 and R 0'may be the same or different, and are selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group and a benzyl group, respectively. m is an integer of 2-4. More preferably, R 0 and R 0 'is selected from a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, m is 2.

前記炭素数１〜８のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、ヘキシル基、シクロヘキシル基などが挙げられる。また、前記炭素数１〜８のアルキル基を有する有機基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基などが挙げられる。前記フェニル基を有する有機基としては、ベンジル基、フェネチル基などが挙げられる。 Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group and a cyclohexyl group. Examples of the organic group having an alkyl group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group and a butoxy group. Examples of the organic group having a phenyl group include a benzyl group and a phenethyl group.

上述したオキシアルキレン基としては、オキシエチレン基、オキシプロピレン基、及びオキシブチレン基が好ましく、オキシエチレン基が特に好ましい。 As the above-mentioned oxyalkylene group, an oxyethylene group, an oxypropylene group, and an oxybutylene group are preferable, and an oxyethylene group is particularly preferable.

上述したオキシアルキレン基は、ポリアセタールコポリマー（Ｘ）中に、１種類あるいは２種類以上含んでいてよい。すなわち、本発明のポリアセタールコポリマー（Ｘ）は、２元共重合体のみならず、多元共重合体も含む。 The above-mentioned oxyalkylene group may be contained in one kind or two or more kinds in the polyacetal copolymer (X). That is, the polyacetal copolymer (X) of the present invention contains not only a binary copolymer but also a multiple copolymer.

また本発明のポリアセタールコポリマー（Ｘ）は、オキシメチレン基、オキシアルキレン基以外のブロック構造をさらに有するポリアセタールコポリマーであってもよく、あるいは、分子内に分岐構造をさらに有するポリアセタールコポリマーであってもよい。これらのポリアセタールコポリマーとしては、例えば、水酸基のような活性水素を有する官能基を分子末端又は分子中に有する熱可塑性樹脂やオリゴマーを連鎖移動剤として用いることによって得られる末端に前記連鎖移動剤の構造が導入されたポリアセタールコポリマー、ポリビニルホルマールのような共重合反応性を有する環状ホルマール部位を主鎖中に含む化合物の存在下で重合反応を行うことによって得られるポリアセタールコポリマーが挙げられる。 Further, the polyacetal copolymer (X) of the present invention may be a polyacetal copolymer further having a block structure other than an oxymethylene group and an oxyalkylene group, or may be a polyacetal copolymer further having a branched structure in the molecule. .. These polyacetal copolymers include, for example, the structure of the chain transfer agent at the terminal obtained by using a thermoplastic resin or an oligomer having a functional group having active hydrogen such as a hydroxyl group at the molecular end or in the molecule as the chain transfer agent. Examples thereof include a polyacetal copolymer in which the above is introduced, and a polyacetal copolymer obtained by carrying out a polymerization reaction in the presence of a compound having a cyclic formal moiety having a copolymerization reactivity such as polyvinyl formal in the main chain.

本発明のポリアセタールコポリマー（Ｘ）は、ターモノマーとしてグリシジルエーテルのようなエポキシ化合物やアリルエーテルなどを用いて製造したものであってよく、ポリアセタールコポリマー中にこれらの化合物に由来する構造を有しているものも含まれる。 The polyacetal copolymer (X) of the present invention may be produced by using an epoxy compound such as glycidyl ether or an allyl ether as a tar monomer, and has a structure derived from these compounds in the polyacetal copolymer. Some are included.

一般にポリアセタールコポリマー中のオキシアルキレン基の含有量（オキシアルキレン基のモル量）は、オキシメチレン基のモル量とオキシアルキレン基のモル量の合計値に対して０．０１〜２０ｍｏｌ％と幅広い範囲であるが、本発明のポリアセタールコポリマー（Ｘ）中のオキシアルキレン基の含有量（オキシアルキレン基のモル量）は、オキシメチレン基のモル量とオキシアルキレン基のモル量の合計値に対して通常０．２〜５ｍｏｌ％であり、好ましくは０．２〜３．０ｍｏｌ％であり、より好ましくは０．２〜２．０ｍｏｌ％であり、特に好ましくは０．２〜１．０ｍｏｌ％である。前記オキシアルキレン基の含有量が０．２ｍｏｌ％以上、５ｍｏｌ％以下であれば、抗菌性が優れ、抗菌性を表す静菌活性値が高く、洗濯を繰り返し行っても静菌活性値が低下しにくい。また、前記オキシアルキレン基の含有量が０．２ｍｏｌ％以上、３．０ｍｏｌ％以下であれば、抗菌性がより優れ、抗菌性を表す静菌活性値がより高く、洗濯を繰り返し行っても静菌活性値がより低下しにくい。 Generally, the content of oxyalkylene groups (molar amount of oxyalkylene groups) in the polyacetal copolymer is in a wide range of 0.01 to 20 mol% with respect to the total value of the molar amount of oxymethylene groups and the molar amount of oxyalkylene groups. However, the content of the oxyalkylene group (molar amount of the oxyalkylene group) in the polyacetal copolymer (X) of the present invention is usually 0 with respect to the total value of the molar amount of the oxymethylene group and the molar amount of the oxyalkylene group. It is 2 to 5 mol%, preferably 0.2 to 3.0 mol%, more preferably 0.2 to 2.0 mol%, and particularly preferably 0.2 to 1.0 mol%. When the content of the oxyalkylene group is 0.2 mol% or more and 5 mol% or less, the antibacterial property is excellent, the bacteriostatic activity value indicating the antibacterial property is high, and the bacteriostatic activity value decreases even after repeated washing. Hateful. Further, when the content of the oxyalkylene group is 0.2 mol% or more and 3.0 mol% or less, the antibacterial property is more excellent, the bacteriostatic activity value indicating the antibacterial property is higher, and the washing is static even after repeated washing. Bacterial activity value is less likely to decrease.

本発明のポリアセタールコポリマー（Ｘ）は、１種類を単独で用いてもよく、オキシアルキレン基の種類が異なるポリアセタールコポリマーを２種類以上組合せて用いてもよく、オキシアルキレン基の含有量が異なるポリアセタールコポリマーを２種類以上組合せて用いてもよい。オキシアルキレン基の種類あるいはオキシアルキレン基の含有量が異なる２種類以上のポリアセタールコポリマーを組合せて用いる場合は、これらのポリアセタールコポリマーが相溶した状態であってよく、海島構造またはそれに由来した分散状態となっている状態であってよく、サイドバイサイドのような状態であってもよい。 As the polyacetal copolymer (X) of the present invention, one type may be used alone, or two or more types of polyacetal copolymers having different types of oxyalkylene groups may be used in combination, and polyacetal copolymers having different oxyalkylene group contents may be used. May be used in combination of two or more types. When two or more types of polyacetal copolymers having different types of oxyalkylene groups or different contents of oxyalkylene groups are used in combination, these polyacetal copolymers may be in a compatible state, and may be in a state of being compatible with the sea-island structure or a dispersed state derived from the polyacetal group. It may be in a state of being in a state of being, and may be in a state of being side-by-side.

本発明のポリアセタールコポリマー（Ｘ）は、ＩＳＯ１１３３に則ったＭＶＲ(Ｍｅｌｔ Ｖｏｌｕｍｅ Ｒａｔｅ)が１００ｃｍ３／１０分以下であることが好ましい。ＭＶＲ値が大きいほど溶融紡糸において細い繊維を得るのに適しているが、１００ｃｍ３／１０分以下であれば、機械物性（特に靭性）に優れた繊維が得られる。Polyacetal copolymer of the present invention (X) is preferably MVR in conformity with ISO1133 (Melt Volume Rate) is less than 100 cm 3/10 min. Although MVR value is suitable for obtaining thin fibers in higher melt spinning greater, equal to or less than 100 cm 3/10 min, fibers having excellent mechanical properties (especially toughness) is obtained.

＜ポリアセタールコポリマー（Ｘ）の製造方法＞
本発明のポリアセタールコポリマー（Ｘ）の製造方法は任意であり、従来公知の任意の方法によって製造すればよい。例えば、オキシメチレン基と、炭素数２以上４以下のオキシアルキレン基を構成単位とするポリアセタール樹脂の製造方法としては、ホルムアルデヒドの３量体（トリオキサン）や４量体（テトラオキサン）等のオキシメチレン基の環状アセタールと、エチレンオキシド、１，３−ジオキソラン、１，３，６−トリオキソカン、１，３−ジオキセパン等の炭素数２以上４以下のオキシアルキレン基を含む環状アセタールとを共重合することによって製造することができる。中でも本発明のポリアセタールコポリマー（Ｘ）としては、トリオキサンやテトラオキサン等の環状アセタールと、エチレンオキシド又は１，３−ジオキソランとの共重合体であることが好ましく、中でもトリオキサンと１，３−ジオキソランとの共重合体であることが特に好ましい。<Manufacturing method of polyacetal copolymer (X)>
The method for producing the polyacetal copolymer (X) of the present invention is arbitrary, and it may be produced by any conventionally known method. For example, as a method for producing a polyacetal resin containing an oxymethylene group and an oxyalkylene group having 2 or more and 4 or less carbon atoms as a constituent unit, an oxymethylene group such as a trimester (trioxane) or a tetramer (tetraoxane) of formaldehyde Is produced by copolymerizing the cyclic acetal of the above with a cyclic acetal containing an oxyalkylene group having 2 to 4 carbon atoms such as ethylene oxide, 1,3-dioxolane, 1,3,6-trioxocan, and 1,3-dioxepan. can do. Among them, the polyacetal copolymer (X) of the present invention is preferably a copolymer of cyclic acetal such as trioxane or tetraoxane with ethylene oxide or 1,3-dioxolane, and above all, a copolymer of trioxane and 1,3-dioxolane. It is particularly preferably a copolymer.

例えば、本発明のポリアセタールコポリマー（Ｘ）は、オキシメチレン基の環状アセタールと、コモノマーである炭素数２以上４以下のオキシアルキレン基を含む環状アセタールとを、重合触媒を用いて塊状重合させる方法で得ることができる。重合触媒及び重合成長末端の失活処理のために、必要に応じて反応停止剤を用いてもよい。また、ポリアセタールコポリマーの分子量調節のために、必要に応じて分子量調節剤を用いてもよい。本発明のポリアセタールコポリマー（Ｘ）の製造に用いることができる重合触媒、反応停止剤、分子量調節剤の種類や量は、本発明の効果を阻害しない限りにおいては特に限定されるものではなく、従来公知の任意の重合触媒、反応停止剤、分子量調節剤を適宜使用することができる。 For example, the polyacetal copolymer (X) of the present invention is a method in which a cyclic acetal having an oxymethylene group and a cyclic acetal containing an oxyalkylene group having 2 to 4 carbon atoms, which is a comonomer, are bulk-polymerized using a polymerization catalyst. Obtainable. If necessary, a reaction terminator may be used for the deactivation treatment of the polymerization catalyst and the polymerization growth terminal. In addition, a molecular weight modifier may be used as needed to regulate the molecular weight of the polyacetal copolymer. The types and amounts of the polymerization catalyst, reaction terminator, and molecular weight modifier that can be used in the production of the polyacetal copolymer (X) of the present invention are not particularly limited as long as the effects of the present invention are not impaired. Any known polymerization catalyst, reaction terminator, and molecular weight modifier can be appropriately used.

前記重合触媒としては特に限定されるものではないが、例えば、三フッ化ホウ素、四塩化スズ、四塩化チタン、五塩化リン、五フッ化リン、五フッ化ヒ素、及び五フッ化アンチモンなどのルイス酸、並びにこれらルイス酸の錯化合物または塩化合物が挙げられる。また、トリフルオロメタンスルホン酸、パークロル酸などのプロトン酸；パークロル酸と低級脂肪族アルコールのエステルなどのプロトン酸のエステル；パークロル酸と低級脂肪族カルボン酸との混合無水物などのプロトン酸の無水物なども挙げられる。このほかに、トリエチルオキソニウムヘキサフルオロホスファート、トリフェニルメチルヘキサフルオロアルゼナート、アセチルヘキサフルオロボラート、ヘテロポリ酸またはその酸性塩、イソポリ酸またはその酸性塩、パーフルオロアルキルスルホン酸またはその酸性塩などが挙げられる。中でも、三フッ化ホウ素を含む化合物が好ましく、エ−テル類との配位錯体である三フッ化ホウ素ジエチルエーテラート、三フッ化ホウ素ジブチルエーテラートが特に好ましい。 The polymerization catalyst is not particularly limited, but for example, boron trifluoride, tin tetrachloride, titanium tetrachloride, phosphorus pentachloride, phosphorus pentafluoride, arsenic pentafluoride, antimony pentafluoride and the like. Lewis acids, as well as complex or salt compounds of these Lewis acids. Also, protonic acids such as trifluoromethanesulfonic acid and perchloric acid; esters of protonic acids such as esters of percorolic acid and lower aliphatic alcohols; anhydrides of protonic acids such as mixed anhydrides of percorolic acid and lower aliphatic carboxylic acids. And so on. In addition, triethyloxonium hexafluorophosphate, triphenylmethylhexafluoroarzenate, acetylhexafluoroborate, heteropolyacid or its acid salt, isopolyacid or its acid salt, perfluoroalkyl sulfonic acid or its acid salt, etc. Can be mentioned. Among them, a compound containing boron trifluoride is preferable, and boron trifluoride diethyl etherate and boron trifluoride dibutyl etherate, which are coordination complexes with ethers, are particularly preferable.

前記重合触媒の使用量は特に限定されるものではないが、トリオキサンとコモノマーの合計の全モノマー１ｍｏｌに対して、通常１．０×１０−8〜２．０×１０−３ｍｏｌであり、好ましくは５．０×１０−8〜８．０×１０−４ｍｏｌ、特に好ましくは５．０×１０−8〜１．０×１０−４ｍｏｌの範囲である。The amount of the polymerization catalyst used is not particularly limited, but is usually 1.0 × 10-8 to 2.0 × 10 -3 mol, preferably 1.0 × 10-8 to 2.0 × 10 -3 mol, based on 1 mol of the total monomer of trioxane and comonomer. Is in the range of 5.0 × 10 −8 to 8.0 × 10 -4 mol, particularly preferably in the range of 5.0 × 10 −8 to 1.0 × 10 -4 mol.

前記反応停止剤としては特に限定されるものではないが、例えば、三価の有機リン化合物、アミン化合物、アルカリ金属又はアルカリ土類金属の水酸化物が挙げられる。これらの反応停止剤は、１種を単独で、または２種以上を組み合わせて使用できる。中でも、三価の有機リン化合物、三級アミン、ヒンダードアミンが好ましい。 The reaction terminator is not particularly limited, and examples thereof include trivalent organic phosphorus compounds, amine compounds, alkali metals, and hydroxides of alkaline earth metals. These reaction terminators can be used alone or in combination of two or more. Of these, trivalent organic phosphorus compounds, tertiary amines and hindered amines are preferable.

前記反応停止剤の使用量は、重合触媒を失活させるのに十分な量であれば特に制限はないが、重合触媒に対するモル比として、通常１．０×１０−１〜１．０×１０１の範囲である。The amount of the reaction terminator used is not particularly limited as long as it is sufficient to inactivate the polymerization catalyst, but the molar ratio to the polymerization catalyst is usually 1.0 × 10 -1 to 1.0 × 10. It is in the range of 1 .

前記分子量調節剤としては特に限定されるものではないが、例えば、メチラール、メトキシメチラール、ジメトキシメチラール、トリメトキシメチラール、オキシメチレンジ−ｎ−ブチルエーテルなどが挙げられる。中でもメチラールが好ましい。これらの分子量調節剤の使用量は、目標とする分子量に応じて適宜決められる。通常、全モノマーに対して０〜０．１質量％の範囲で添加量が調整される。 The molecular weight regulator is not particularly limited, and examples thereof include methylal, methoxymethylal, dimethoxymethylal, trimethoxymethylal, and oxymethylene di-n-butyl ether. Of these, methylal is preferable. The amount of these molecular weight modifiers used is appropriately determined according to the target molecular weight. Usually, the addition amount is adjusted in the range of 0 to 0.1% by mass with respect to all the monomers.

＜ポリアセタールコポリマー（Ｘ）に含まれてよい、任意成分、その他の成分＞
また、本発明を実施するとき、本発明のポリアセタールコポリマー（Ｘ）には、本来の目的を損なわない範囲内で、ヒンダードフェノール化合物、ヒンダードアミン化合物、アミノ置換トリアジン化合物、リン系安定剤、アルカリ金属及びアルカリ土類金属の水酸化物、脂肪酸塩、無機酸塩、又はアルコキシドからなる群で示される金属含有化合物を添加することができる。以下、本明細書では、上述した「ヒンダードフェノール化合物、ヒンダードアミン化合物、アミノ置換トリアジン化合物、リン系安定剤、アルカリ金属及びアルカリ土類金属の水酸化物、脂肪酸塩、無機酸塩、又はアルコキシドからなる群で示される金属含有化合物」のことを「任意成分」ということもある。これらの任意成分としては、従来公知のものを使用することができる。<Arbitrary components and other components that may be contained in the polyacetal copolymer (X)>
Further, when the present invention is carried out, the polyacetal copolymer (X) of the present invention contains a hindered phenol compound, a hindered amine compound, an amino-substituted triazine compound, a phosphorus-based stabilizer, and an alkali metal within a range that does not impair the original purpose. And metal-containing compounds represented by the group consisting of hydroxides, fatty acid salts, inorganic acid salts, or alkoxides of alkaline earth metals can be added. Hereinafter, in the present specification, from the above-mentioned "hindered phenol compound, hindered amine compound, amino-substituted triazine compound, phosphorus-based stabilizer, hydroxide of alkali metal and alkaline earth metal, fatty acid salt, inorganic acid salt, or alkoxide". The "metal-containing compound represented by the group" may be referred to as an "arbitrary component". As these optional components, conventionally known components can be used.

また、本発明を実施するとき、本発明のポリアセタールコポリマー（Ｘ）には、本来の目的を損なわない範囲内で、上述した任意成分の他に、必要に応じて安定剤、核化剤、離型剤、充填剤、顔料、染料、滑剤、可塑剤、帯電防止剤、油剤、集束剤、紫外線吸収剤、難燃剤、難燃助剤、抗カビ剤、抗ウィルス剤などの各種添加剤、他の樹脂、エラストマーなどを適宜添加してもよい。以下、本明細書では、上述した「安定剤、核化剤、離型剤、充填剤、顔料、染料、滑剤、可塑剤、帯電防止剤、油剤、集束剤、紫外線吸収剤、難燃剤、難燃助剤、抗カビ剤、抗ウィルス剤などの各種添加剤、他の樹脂、エラストマーなど」のことを「その他の成分」ということもある。充填剤としてはガラス繊維、ガラスフレーク、ガラスビーズ、ウオラストナイト、マイカ、タルク、窒化ホウ素、炭酸カルシウム、カオリン、二酸化珪素、クレー、アスベスト、シリカ、ケイソウ土、グラファイト、二硫化モリブデンなどの鉱物質充填剤及びガラス繊維、ミドルファイバー、チタン酸カリウム繊維、ポロン繊維などの無機繊維、並びに炭素繊維、アラミド繊維に代表される有機繊維、チタン酸カリウムウィスカー、さらに、カーボンブラック、顔料等を挙げることができる。 Further, when the present invention is carried out, the polyacetal copolymer (X) of the present invention contains a stabilizer, a nucleating agent, and a release agent, if necessary, in addition to the above-mentioned optional components, as long as the original purpose is not impaired. Molds, fillers, pigments, dyes, lubricants, plasticizers, antioxidants, oils, sizing agents, UV absorbers, flame retardants, flame retardants, various additives such as antifungal agents, antiviral agents, etc. Resin, elastomer and the like may be added as appropriate. Hereinafter, in the present specification, the above-mentioned "stabilizer, nucleating agent, mold release agent, filler, pigment, dye, lubricant, plasticizer, antistatic agent, oil agent, sizing agent, ultraviolet absorber, flame retardant, difficulty "Various additives such as flame retardants, antifungal agents, antiviral agents, other resins, elastomers, etc." may also be referred to as "other components". As fillers, mineral substances such as glass fiber, glass flakes, glass beads, wolastonite, mica, talc, boron nitride, calcium carbonate, kaolin, silicon dioxide, clay, asbestos, silica, silica soil, graphite, molybdenum disulfide, etc. Inorganic fibers such as fillers and glass fibers, middle fibers, potassium titanate fibers, and polon fibers, organic fibers typified by carbon fibers and aramid fibers, potassium titanate whisker, carbon black, pigments, etc. may be mentioned. it can.

上述した任意成分やその他の成分を、ポリアセタールコポリマー（Ｘ）へ添加する方法は、特に限定されるものではなく、例えば、上記したポリアセタールコポリマー（Ｘ）と必要に応じて添加される任意成分及び／又はその他の成分を、任意の順序で混合、混練することによって製造できる。混合・混練の温度、圧力等の条件は、従来公知のポリアセタールコポリマーの製造方法にしたがって適宜選択すればよい。例えば、混練はポリアセタールコポリマーの溶融温度以上で行えばよく、通常は１８０℃以上２６０℃以下で行うのが好ましい。ポリアセタールコポリマーの製造装置も特に限定されるものではなく、従来からこの種のポリアセタールコポリマーの製造に用いられている混合、混練装置などを用いることができる。なお、上述した任意成分やその他の成分は、ポリアセタールコポリマー（Ｘ）を含有する繊維に別途、混合、浸透、吸着、付着させてもよい。 The method for adding the above-mentioned optional components and other components to the polyacetal copolymer (X) is not particularly limited, and for example, the above-mentioned optional components and / or optional components added as needed with the polyacetal copolymer (X). Alternatively, other components can be produced by mixing and kneading in any order. Conditions such as mixing / kneading temperature and pressure may be appropriately selected according to a conventionally known method for producing a polyacetal copolymer. For example, kneading may be performed at a temperature equal to or higher than the melting temperature of the polyacetal copolymer, and is usually preferably performed at 180 ° C. or higher and 260 ° C. or lower. The apparatus for producing the polyacetal copolymer is not particularly limited, and a mixing and kneading apparatus conventionally used for producing this type of polyacetal copolymer can be used. In addition, the above-mentioned optional component and other components may be separately mixed, permeated, adsorbed, and adhered to the fiber containing the polyacetal copolymer (X).

＜抗菌用繊維の用途＞
本発明の抗菌用繊維は、用途に応じて不織布、織物、編物、フェルト、ウェブなどの形態に加工することができる。特に抗菌性を活かすために好適な形態は、不織布からなるフィルターである。これら不織布、織物、編物、フェルト、ウェブも本発明の抗菌用繊維と同等の抗菌性を有し、洗濯を繰り返しても抗菌性が持続するという優れた特徴を有する。また、従来の有機系抗菌剤や無機系抗菌剤を有する抗菌用繊維に比べて、加工時の耐熱性や変色などの問題がなく、安全性に優れるため、幅広い用途において好適に用いることができる。特に、本発明の不織布は、フィルターとして好適に使用することができる。このフィルターも本発明の抗菌用繊維と同等の抗菌性を有し、洗濯を繰り返しても抗菌性が持続するという優れた特徴を有する。また、本発明の織物、編物、フェルト、及びウェブは、肌着、シャツ、スポーツウェア、エプロン、ソックス、ストッキング、タイツ、パンティストッキング、足袋、和装品、ネクタイ、ハンカチ、スカーフ、帽子、手袋、マスク、おむつなどの衣料、枕カバー、タオルケット、シーツ、布団中わたなどの寝具、カーテン、カーぺット、マット、ラグ、壁掛け、壁張り、テーブルクロス、モケットなどのインテリア具、タオル、ふきん、たわし、モップ、ぬいぐるみの中わたなどの雑貨などに好適に使用することができる。これらの衣料、寝具、インテリア具、及び雑貨も本発明の抗菌用繊維と同等の抗菌性を有し、洗濯を繰り返しても抗菌性が持続するという優れた特徴を有する。<Use of antibacterial fiber>
The antibacterial fiber of the present invention can be processed into a non-woven fabric, a woven fabric, a knitted fabric, a felt, a web, or the like depending on the intended use. A particularly suitable form for utilizing the antibacterial property is a filter made of a non-woven fabric. These non-woven fabrics, woven fabrics, knitted fabrics, felts, and webs also have the same antibacterial properties as the antibacterial fibers of the present invention, and have an excellent feature that the antibacterial properties are maintained even after repeated washing. In addition, compared to conventional antibacterial fibers having an organic antibacterial agent or an inorganic antibacterial agent, there are no problems such as heat resistance and discoloration during processing, and the safety is excellent, so that it can be suitably used in a wide range of applications. .. In particular, the non-woven fabric of the present invention can be suitably used as a filter. This filter also has the same antibacterial property as the antibacterial fiber of the present invention, and has an excellent feature that the antibacterial property is maintained even after repeated washing. The woven fabrics, knitted fabrics, felts, and webs of the present invention include underwear, shirts, sportswear, aprons, socks, stockings, tights, panty stockings, socks, Japanese clothing, ties, handkerchiefs, scarves, hats, gloves, masks, etc. Clothing such as diapers, pillowcases, towelettes, sheets, bedding such as duvets, curtains, carpets, mats, rugs, wall hangings, wall coverings, table cloths, moquette and other interior items, towels, towels, wadding, It can be suitably used for miscellaneous goods such as mops and stuffed clothes. These clothing, bedding, interior goods, and miscellaneous goods also have the same antibacterial properties as the antibacterial fibers of the present invention, and have an excellent feature that the antibacterial properties are maintained even after repeated washing.

また、本発明の抗菌用繊維を用いて不織布、織物、編物、フェルト、ウェブなどの形態に加工する際、本発明の抗菌用繊維のみを用いて加工してもよいが、ナイロン、ポリエステル、ポリウレタンなどの合成繊維、木綿や絹糸などの天然繊維、炭素繊維、ガラス繊維などと複合させて、合撚糸、カバリング糸、組紐として、不織布、織物、編物、フェルト、ウェブなどの形態に加工してもよく、ナイロンやポリエステル、ポリウレタンなどの合成繊維、木綿や絹糸などの天然繊維、炭素繊維、ガラス繊維と混繊、混紡して、不織布、織物、編物、フェルト、ウェブなどの形態に加工してもよい。また、本発明の抗菌用繊維又は用途に応じて織物、編物などに加工された形態において、更に染色や種々の仕上げ加工（防しわ、防汚、難燃、防虫、防カビ、防臭、吸湿、防水、艶出し、抗ピルなど）を行うことにより、抗菌性以外の機能を付与することができる。 Further, when processing into a non-woven fabric, woven fabric, knitted fabric, felt, web or the like using the antibacterial fiber of the present invention, it may be processed using only the antibacterial fiber of the present invention, but nylon, polyester, polyurethane. Synthetic fibers such as, natural fibers such as cotton and silk, carbon fibers, glass fibers, etc. can be combined and processed into non-woven fabrics, textiles, knitted fabrics, felts, webs, etc. as twisted yarns, covering yarns, braids. Often, synthetic fibers such as nylon, polyester and polyurethane, natural fibers such as cotton and silk thread, carbon fibers, and glass fibers are mixed and blended to form non-woven fabrics, textiles, knitted fabrics, felts, webs, etc. Good. Further, in the form of the antibacterial fiber of the present invention or processed into a woven fabric, knitted fabric, etc. according to the application, further dyeing and various finishing processes (wrinkle-proof, stain-proof, flame-retardant, insect-proof, mold-proof, deodorant, moisture absorption, etc. By performing waterproofing, polishing, anti-pill, etc.), functions other than antibacterial properties can be imparted.

本発明の抗菌性を有する不織布の製造方法は特に限定されるものではなく、従来公知の乾式法、湿式法、スパンボンド法、メルトブロー法などを用いることができる。このとき、繊維同士を十分に結合もしくは絡合させることで繊維の脱落を抑制するのが好ましい。そのような方法としては、サーマルボンド法、ケミカルボンド法、ニードルパンチ法、スパンレース法（水流絡合法）、ステッチボンド法、スチームジェット法などが挙げられ、その中でもサーマルボンド法が十分な結合を達成できるため好ましい。 The method for producing the non-woven fabric having antibacterial properties of the present invention is not particularly limited, and conventionally known dry methods, wet methods, spunbond methods, melt blow methods and the like can be used. At this time, it is preferable to suppress the fibers from falling off by sufficiently binding or entwining the fibers. Examples of such a method include a thermal bond method, a chemical bond method, a needle punch method, a spunlace method (water flow entanglement method), a stitch bond method, and a steam jet method. Among them, the thermal bond method provides sufficient bonding. It is preferable because it can be achieved.

また、上述の不織布からなるフィルターを支持するフレーム部材に対してもポリアセタールコポリマー（Ｘ）を使用することで抗菌性、リサイクル性に優れた製品となる。 Further, by using the polyacetal copolymer (X) for the frame member supporting the filter made of the above-mentioned non-woven fabric, the product has excellent antibacterial properties and recyclability.

以下、本発明について実施例、比較例を示して、その実施形態と効果について具体的に説明をするが、本発明はこれらの例によりなんら限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, and the embodiments and effects thereof will be specifically described, but the present invention is not limited to these examples.

＜ポリアセタールコポリマー＞
実施例及び比較例で用いたポリアセタールコポリマーは、以下のとおりである。なお、ポリアセタールコポリマー（Ｘ）中のオキシエチレン基の含有量（オキシエチレン基のモル量）は、オキシメチレン基のモル量とオキシエチレン基のモル量の合計値に対する値である。
ＰＯＭ−１：オキシエチレン基の含有量が０．４ｍｏｌ％であり、ＭＶＲが８であるポリアセタールコポリマー。
ＰＯＭ−２：オキシエチレン基の含有量が１．６ｍｏｌ％であり、ＭＶＲが８であるポリアセタールコポリマー。
ＰＯＭ−３：オキシエチレン基の含有量が３．０ｍｏｌ％であり、ＭＶＲが８であるポリアセタールコポリマー。
ＰＯＭ−４：オキシエチレン基の含有量が４．７ｍｏｌ％であり、ＭＶＲが８であるポリアセタールコポリマー。
ＰＯＭ−５：オキシエチレン基の含有量が５．７ｍｏｌ％であり、ＭＶＲが８であるポリアセタールコポリマー。<Polyacetal copolymer>
The polyacetal copolymers used in Examples and Comparative Examples are as follows. The content of oxyethylene groups (molar amount of oxyethylene groups) in the polyacetal copolymer (X) is a value with respect to the total value of the molar amount of oxymethylene groups and the molar amount of oxyethylene groups.
POM-1: A polyacetal copolymer having an oxyethylene group content of 0.4 mol% and an MVR of 8.
POM-2: A polyacetal copolymer having an oxyethylene group content of 1.6 mol% and an MVR of 8.
POM-3: A polyacetal copolymer having an oxyethylene group content of 3.0 mol% and an MVR of 8.
POM-4: A polyacetal copolymer having an oxyethylene group content of 4.7 mol% and an MVR of 8.
POM-5: A polyacetal copolymer having an oxyethylene group content of 5.7 mol% and an MVR of 8.

＜その他の熱可塑性樹脂＞
ＰＬＡ（ポリ乳酸樹脂）：ユニチカ株式会社製テラマック（登録商標）ＴＥ２０００をそのまま用いた。
ＰＥＴ（ポリエチレンテレフタレート樹脂）：単繊度２デシテックスのマルチフィラメントをそのまま用いた。<Other thermoplastic resins>
PLA (polylactic acid resin): TE2000 (registered trademark) manufactured by Unitika Ltd. was used as it was.
PET (polyethylene terephthalate resin): A multifilament having a single fineness of 2 decitex was used as it was.

＜ＭＶＲの測定＞
ポリアセタールコポリマーのＭＶＲ（ｃｍ３／１０分）は、ＩＳＯ１１３３に従って測定した。<Measurement of MVR>
The polyacetal copolymer MVR (cm 3/10 min) was measured according to ISO 1133.

＜ポリアセタールコリマー中のオキシエチレン基の含有量の測定＞
実施例及び比較例で用いたポリアセタールコポリマーをヘキサフルオロイソプロパノール（ｄ２）に溶解させて、ＮＭＲ測定試料を作製し、この測定試料についてＮＭＲスペクトルを測定して、ポリアセタールコポリマー中のオキシエチレン基の含有量を測定した。<Measurement of oxyethylene group content in polyacetal colimer>
The polyacetal copolymer used in Examples and Comparative Examples was dissolved in hexafluoroisopropanol (d2) to prepare an NMR measurement sample, and the NMR spectrum of this measurement sample was measured to determine the content of oxyethylene groups in the polyacetal copolymer. Was measured.

＜繊維の繊度測定＞
繊維の繊度［ｄｔｅｘ（デシテックス）］は、光学顕微鏡を用いて単繊維の繊径を測定し、密度１．４０ｇ／ｃｍ３として繊度を算出し、測定本数５０本の平均値を繊維の繊度とした。<Measurement of fiber fineness>
For the fiber fineness [dtex], the fineness of a single fiber is measured using an optical microscope, the fineness is calculated with a density of 1.40 g / cm 3 , and the average value of 50 measured fibers is taken as the fineness of the fiber. did.

＜繊維の配向度ｆｃ（％）測定＞
広角Ｘ線回折装置（株式会社島津製作所製 ＤＰ−Ｄ１）を用い、ＣｕＫα（Ｎｉフイルターを使用）を線源として測定した（出力４５ＫＶ、４０ｍＡ）。配向度（ｆｃ）は、２θ＝２２．２°付近に観察される（１００）面について、円周方向にスキャンして得られる回折強度の分布曲線（方位角分布曲線）の半値幅ＦＷＨＭ（°）から、下記の式（１）を用いて求めた。
<Measurement of fiber orientation fc (%)>
Measurement was performed using a wide-angle X-ray diffractometer (DP-D1 manufactured by Shimadzu Corporation) using CuKα (using a Ni filter) as a radiation source (output 45 KV, 40 mA). The degree of orientation (fc) is the half width FWHM (°) of the diffraction intensity distribution curve (azimuth angle distribution curve) obtained by scanning the (100) plane observed in the vicinity of 2θ = 22.2 ° in the circumferential direction. ), Using the following formula (1).

＜繊維試料の作成＞
シリンダー、ノズル部の温度を２００℃に加温し、直径が０．６ｍｍのホールを４８個備えたノズルから１．２ｋｇ/ｈの速度で、溶融樹脂を吐出した。なお、芯鞘複合繊維の場合は、ノズルからの吐出速度は、芯成分の樹脂、鞘成分の樹脂ともに０．６ｋｇ/ｈとした。この時、引取り速度を１００ｍ／分に固定して連続的に未延伸繊維を採取し、得られた未延伸繊維を引き続き加熱延伸工程へ導き、ロール温度１２０〜１４０℃で延伸処理を行って繊維試料を作成した。<Preparation of fiber sample>
The temperature of the cylinder and the nozzle portion was heated to 200 ° C., and the molten resin was discharged at a speed of 1.2 kg / h from a nozzle provided with 48 holes having a diameter of 0.6 mm. In the case of the core-sheath composite fiber, the discharge speed from the nozzle was 0.6 kg / h for both the core component resin and the sheath component resin. At this time, the take-up speed was fixed at 100 m / min, undrawn fibers were continuously collected, the obtained undrawn fibers were continuously guided to the heat drawing step, and the drawing treatment was performed at a roll temperature of 120 to 140 ° C. A fiber sample was prepared.

＜不織布及びフィルターの作成＞
上記延伸繊維に捲縮処理を施した後、５１ｍｍ長にカットした。これをカード機（株式会社京和機材製作所製）でウェブとし、ニードルパンチ装置（有限会社大和機工社製）で交絡させてニードルパンチ不織布とした。<Creation of non-woven fabric and filter>
After the drawn fiber was crimped, it was cut into a length of 51 mm. This was made into a web with a card machine (manufactured by Kyowa Kikai Seisakusho Co., Ltd.) and entangled with a needle punching device (manufactured by Daiwa Kiko Co., Ltd.) to form a needle punched non-woven fabric.

＜抗菌性試験（静菌活性値、殺菌活性値、洗濯１０回後の静菌活性保持率、洗濯１０回後の殺菌活性保持率）＞
ＪＩＳ Ｌ １９０２（繊維製品の抗菌性試験方法及び抗菌効果）に準拠し、定量試験（菌液吸収法）により評価した。標準綿布の繊維試料、実施例又は比較例の繊維試料（以下、測定試料という）０．４ｇをそれぞれ別々のバイアル瓶に入れ、試験菌液０．２ｍｌを接種し、３７±２℃で１８±１時間培養した後、非イオン界面活性剤０．２％を含む生理食塩水２０ｍｌを加えて試料から菌を洗い出し、洗い出し液中の菌数を混釈平板培養法（コロニー法）により測定し、下記の式（２）に従い静菌活性値を算出した。静菌活性値の数値が大きいほど、抗菌性に優れる。また、黄色ブドウ球菌に対する静菌活性値が２．２以上であれば、一般社団法人繊維評価技術協議会が認証するＳＥＫマーク（青：抗菌防臭加工）に該当する。また、下記の式（３）に従って殺菌活性値を算出した。殺菌活性値が大きいほど抗菌性に優れ、０より大きいと抗菌性試験の前後で菌が減少することを意味する。


洗濯１０回後の静菌活性保持率と殺菌活性保持率は、次のようにして求めた。洗濯方法は、ＪＩＳ Ｌ ０２１７の１０３号に準拠し、洗剤はＪＡＦＥＴ標準配合洗剤を用いた。１０回繰り返し洗濯処理を行った後に上述と同じ抗菌性試験を行い、下記の式（４）に従い、洗濯１０回後の静菌活性保持率［単位：％］を算出した。また、下記の式（５）に従い、洗濯１０回後の殺菌活性保持率［単位：％］を算出した。いずれも、数値が１００％に近いほど、抗菌性に優れる。


上記、静菌活性値、殺菌活性値、及び洗濯１０回後の静菌活性保持率、殺菌活性保持率は、黄色ブドウ球菌とモラクセラ菌について測定した。<Antibacterial activity test (bactericidal activity value, bactericidal activity value, bactericidal activity retention rate after 10 washings, bactericidal activity retention rate after 10 washings)>
It was evaluated by a quantitative test (bacterial solution absorption method) in accordance with JIS L 1902 (antibacterial test method and antibacterial effect of textile products). 0.4 g of a standard cotton cloth fiber sample and a fiber sample of Example or Comparative Example (hereinafter referred to as a measurement sample) are placed in separate vials, inoculated with 0.2 ml of the test bacterial solution, and 18 ± at 37 ± 2 ° C. After culturing for 1 hour, 20 ml of physiological saline containing 0.2% of nonionic surfactant was added to wash out the bacteria from the sample, and the number of bacteria in the washing solution was measured by the pour plate culture method (colony method). The bacteriostatic activity value was calculated according to the following formula (2). The larger the bacteriostatic activity value, the better the antibacterial property. If the bacteriostatic activity value against Staphylococcus aureus is 2.2 or more, it corresponds to the SEK mark (blue: antibacterial and deodorant processing) certified by the Textile Evaluation Technology Council. In addition, the bactericidal activity value was calculated according to the following formula (3). The larger the bactericidal activity value, the better the antibacterial property, and when it is larger than 0, it means that the bacteria decrease before and after the antibacterial property test.


The bacteriostatic activity retention rate and the bactericidal activity retention rate after 10 times of washing were determined as follows. The washing method conformed to JIS L 0217 No. 103, and the detergent used was a JAFET standard-blended detergent. After the washing treatment was repeated 10 times, the same antibacterial property test as described above was carried out, and the bacteriostatic activity retention rate [unit:%] after 10 washings was calculated according to the following formula (4). In addition, the bactericidal activity retention rate [unit:%] after 10 washings was calculated according to the following formula (5). In each case, the closer the value is to 100%, the better the antibacterial property.


The above-mentioned bacteriostatic activity value, bactericidal activity value, bacteriostatic activity retention rate and bactericidal activity retention rate after 10 times of washing were measured for Staphylococcus aureus and Moraxella.

＜実施例及び比較例＞
表１に、オキシエチレン基含有量が所定範囲内であるポリアセタールコポリマーの単層繊維、オキシエチレン基含有量が所定範囲内であるポリアセタールコポリマーの多層繊維、オキシエチレン基含有量が所定範囲内であるポリアセタールコポリマーとＰＬＡの多層繊維の実施例、並びにポリエステル繊維、オキシエチレン基含有量が所定範囲よりも多いポリアセタールコポリマー単層繊維の比較例を示した。
それぞれの例につき、ポリアセタールコポリマー中のオキシエチレン含有量、単繊度、配向度と、上述の抗菌性試験における培養後の静菌数（単位：個）、抗菌性試験前後の増加比、静菌活性値、洗濯１０回後の静菌活性保持率、殺菌活性値、洗濯１０回後の殺菌活性維持率を示した。<Examples and Comparative Examples>
In Table 1, the monolayer fibers of the polyacetal copolymer having the oxyethylene group content within the predetermined range, the multilayer fibers of the polyacetal copolymer having the oxyethylene group content within the predetermined range, and the oxyethylene group content are within the predetermined range. Examples of multi-layer fibers of polyacetal copolymer and PLA, and comparative examples of polyester fibers and polyacetal copolymer single-layer fibers having an oxyethylene group content higher than a predetermined range are shown.
For each example, the oxyethylene content, single fineness, and orientation in the polyacetal copolymer, the bacteriostatic number (unit: pieces) after culturing in the above-mentioned antibacterial test, the increase ratio before and after the antibacterial test, and the bacteriostatic activity. The values, the bacteriostatic activity retention rate after 10 times of washing, the bactericidal activity value, and the bactericidal activity maintenance rate after 10 times of washing were shown.

実施例１〜６と比較例１、２より、ポリアセタールコポリマー中のオキシエチレン量が０．２〜５ｍｏｌ％であれば、静菌活性値、殺菌活性値、及び洗濯後の殺菌活性保持率に優れることがわかる。また、実施例４〜６より、繊維中のポリアセタールコポリマーの配向度が高いと、静菌活性値、殺菌活性値、及び洗濯後の殺菌活性保持率が更に優れることがわかる。 From Examples 1 to 6 and Comparative Examples 1 and 2, when the amount of oxyethylene in the polyacetal copolymer is 0.2 to 5 mol%, the bacteriostatic activity value, the bactericidal activity value, and the bactericidal activity retention rate after washing are excellent. You can see that. Further, from Examples 4 to 6, it can be seen that when the degree of orientation of the polyacetal copolymer in the fiber is high, the bacteriostatic activity value, the bactericidal activity value, and the bactericidal activity retention rate after washing are further excellent.

Claims (15)

オキシメチレン基と下記一般式（１）で表されるオキシアルキレン基を有するポリアセタールコポリマー（Ｘ）を表面に有する繊維であって、ポリアセタールコポリマー（Ｘ）中のオキシアルキレン基のモル量が、オキシメチレン基のモル量とオキシアルキレン基のモル量の合計値に対して０．２〜５ｍｏｌ％である、黄色ブドウ球菌及びモラクセラ菌に対する抗菌用繊維。

（式中、Ｒ０及びＲ０’は、同一又は異なってもよく、それぞれ、水素原子、炭素数１〜８のアルキル基、炭素数１〜８のアルキル基を有する有機基、フェニル基、及びフェニル基を有する有機基から選択され、ｍは、２〜６の整数である。） A fiber having a polyacetal copolymer (X) having an oxymethylene group and an oxyalkylene group represented by the following general formula (1) on its surface, and the molar amount of the oxyalkylene group in the polyacetal copolymer (X) is oxymethylene. a 0.2～5Mol% of the total value of the molar amount of the molar amount and the oxyalkylene group radicals, textile antibacterial against Staphylococcus aureus and Moraxella.

(In the formula, R 0 and R 0'may be the same or different, respectively, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an organic group having an alkyl group having 1 to 8 carbon atoms, a phenyl group, and a phenyl group, respectively. Selected from organic groups with phenyl groups, m is an integer of 2-6.) 前記ポリアセタールコポリマー（Ｘ）の配向度が６０％以上である、請求項１に記載の抗菌用繊維。 The antibacterial fiber according to claim 1, wherein the polyacetal copolymer (X) has an orientation degree of 60% or more. 前記ポリアセタールコポリマー（Ｘ）を表面に有する繊維が、ポリアセタールコポリマー（Ｘ）の単層繊維である、請求項１又は２に記載の抗菌用繊維。 The antibacterial fiber according to claim 1 or 2, wherein the fiber having the polyacetal copolymer (X) on its surface is a single-layer fiber of the polyacetal copolymer (X). 前記ポリアセタールコポリマー（Ｘ）を表面に有する繊維が、熱可塑性樹脂からなる繊維をポリアセタールコポリマー（Ｘ）で被覆した多層繊維である、請求項１又は２に記載の抗菌用繊維。 The antibacterial fiber according to claim 1 or 2, wherein the fiber having the polyacetal copolymer (X) on its surface is a multilayer fiber in which a fiber made of a thermoplastic resin is coated with the polyacetal copolymer (X). 前記ポリアセタールコポリマー（Ｘ）を表面に有する繊維が、熱可塑性樹脂からなる繊維の表面にポリアセタールコポリマー（Ｘ）を有する複合繊維である、請求項１又は２に記載の抗菌用繊維。 The antibacterial fiber according to claim 1 or 2, wherein the fiber having the polyacetal copolymer (X) on the surface is a composite fiber having the polyacetal copolymer (X) on the surface of the fiber made of a thermoplastic resin. 前記熱可塑性樹脂が、ポリアセタールホモポリマー、ポリアセタールコポリマー（Ｘ）以外のポリアセタールコポリマー、ポリオレフィン樹脂、ポリ乳酸樹脂、ナイロン樹脂、ポリエステル樹脂、ポリビニル樹脂、及びこれらのエラストマーから選択される１種類又は２種類以上である、請求項４又は５に記載の抗菌用繊維。 One or more of the thermoplastic resins selected from polyacetal homopolymers, polyacetal copolymers other than polyacetal copolymer (X), polyolefin resins, polylactic acid resins, nylon resins, polyester resins, polyvinyl resins, and elastomers thereof. The antibacterial fiber according to claim 4 or 5. 請求項１〜６のいずれか一項に記載の抗菌用繊維を用いた不織布。 A non-woven fabric using the antibacterial fiber according to any one of claims 1 to 6. 請求項７に記載の不織布を用いたフィルター。 The filter using the non-woven fabric according to claim 7. 請求項１〜６のいずれか一項に記載の抗菌用繊維を用いた編物。 A knitted fabric using the antibacterial fiber according to any one of claims 1 to 6. 請求項１〜６のいずれか一項に記載の抗菌用繊維を用いた織物。 A woven fabric using the antibacterial fiber according to any one of claims 1 to 6. 請求項１〜６のいずれか一項に記載の抗菌用繊維を用いたフェルト。 A felt using the antibacterial fiber according to any one of claims 1 to 6. 請求項１〜６のいずれか一項に記載の抗菌用繊維を用いたウェブ。 A web using the antibacterial fiber according to any one of claims 1 to 6. 請求項９〜１２に記載の編物、織物、フェルト、及びウェブからなる群より選択されるいずれか１種以上を用いた衣料。 A garment using any one or more selected from the group consisting of knitted fabrics, woven fabrics, felts, and webs according to claims 9 to 12. 請求項９〜１２に記載の編物、織物、フェルト、及びウェブからなる群より選択されるいずれか１種以上を用いた寝具。 Bedding using any one or more selected from the group consisting of knitted fabrics, woven fabrics, felts, and webs according to claims 9 to 12. 請求項９〜１２に記載の編物、織物、フェルト、及びウェブからなる群より選択されるいずれか１種以上を用いたインテリア具。 An interior tool using any one or more selected from the group consisting of knitted fabrics, woven fabrics, felts, and webs according to claims 9 to 12.
JP2017506489A 2015-03-18 2016-03-10 Antibacterial fiber Active JP6787309B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2015054267 2015-03-18
JP2015054267 2015-03-18
PCT/JP2016/057513 WO2016147998A1 (en) 2015-03-18 2016-03-10 Antimicrobial fiber

Publications (2)

Publication Number Publication Date
JPWO2016147998A1 JPWO2016147998A1 (en) 2017-12-28
JP6787309B2 true JP6787309B2 (en) 2020-11-18

Family

ID=56918820

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2017506489A Active JP6787309B2 (en) 2015-03-18 2016-03-10 Antibacterial fiber

Country Status (7)

Country Link
US (2) US20180080149A1 (en)
EP (1) EP3272917A4 (en)
JP (1) JP6787309B2 (en)
KR (1) KR102551954B1 (en)
CN (1) CN107407010B (en)
TW (1) TWI704259B (en)
WO (1) WO2016147998A1 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016151383A1 (en) * 2015-03-20 2016-09-29 Defente Ruggiero Differentiated lymph drainage garment
US10828587B2 (en) 2015-04-17 2020-11-10 Hollingsworth & Vose Company Stable filter media including nanofibers
EP3351662A4 (en) * 2015-09-18 2018-10-24 Mitsubishi Gas Chemical Company, Inc. Fiber for cool contact sensation and fiber product in which same is used
JP6796068B2 (en) * 2015-09-18 2020-12-02 三菱瓦斯化学株式会社 Fabric with excellent cool contact feeling and dyeing fastness
WO2019012877A1 (en) * 2017-07-14 2019-01-17 三菱瓦斯化学株式会社 Method for manufacturing polyacetal fiber
TWI776002B (en) 2017-12-28 2022-09-01 日商三菱瓦斯化學股份有限公司 Optical resin material and optical element for chromatic aberration correction
US11452959B2 (en) 2018-11-30 2022-09-27 Hollingsworth & Vose Company Filter media having a fine pore size distribution
JP7229800B2 (en) * 2019-02-07 2023-02-28 旭化成株式会社 Polyacetal resin composition

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05230325A (en) 1992-02-24 1993-09-07 Polyplastics Co Antibacterial, antifungal polyacetal resin composition
JPH08144128A (en) * 1994-11-15 1996-06-04 Kanebo Ltd Conjugate fiber and nonwoven fabric and knitted fabric
JPH09291193A (en) 1996-04-24 1997-11-11 Asahi Chem Ind Co Ltd Antifungal polyacetal resin composition
JPH10265585A (en) 1997-03-26 1998-10-06 Polyplastics Co Antimicrobial polyacetal resin composition
JP3542940B2 (en) * 2001-04-27 2004-07-14 日華化学株式会社 Disinfectant, antibacterial agent and antibacterial material
JP4907023B2 (en) * 2001-09-18 2012-03-28 ポリプラスチックス株式会社 Method for producing polyoxymethylene fiber
JP4260392B2 (en) * 2001-12-14 2009-04-30 ポリプラスチックス株式会社 Flat yarn made of polyoxymethylene resin, its production method and use
JP2003268627A (en) * 2002-03-07 2003-09-25 Toray Ind Inc Polyacetal fiber
JP2004360146A (en) * 2003-06-09 2004-12-24 Polyplastics Co Non-woven fabric made from polyoxymethylene resin, and method for producing the same
JP2005013829A (en) * 2003-06-25 2005-01-20 Polyplastics Co Polyoxymethylene resin-made filter
JP4468086B2 (en) * 2004-06-28 2010-05-26 ポリプラスチックス株式会社 Composite fiber made of polyoxymethylene resin
JP2006328322A (en) * 2005-05-30 2006-12-07 Sekisui Chem Co Ltd Curable resin composition for column spacer, column spacer and liquid crystal display element
CN101292064A (en) * 2005-09-15 2008-10-22 纤维创新技术公司 Multicomponent fiber comprising a phase change material
JP5116984B2 (en) * 2006-04-06 2013-01-09 ポリプラスチックス株式会社 Nonwoven fabric and method for producing the same
JP4912768B2 (en) * 2006-06-29 2012-04-11 ポリプラスチックス株式会社 Method for producing polyoxymethylene resin fiber
JP4907307B2 (en) * 2006-11-17 2012-03-28 ポリプラスチックス株式会社 Method for producing polyoxymethylene fiber sewing thread
JP5261924B2 (en) * 2006-12-04 2013-08-14 三菱瓦斯化学株式会社 Oxymethylene copolymer multilayer fiber
JP5261933B2 (en) 2006-12-27 2013-08-14 三菱瓦斯化学株式会社 Oxymethylene composite fiber
US20100190406A1 (en) * 2007-07-19 2010-07-29 Daiwabo Holdings Co., Ltd. Heat-bondable composite fiber, process for producing the same, and fibrous mass
CN102066627B (en) * 2008-05-29 2013-01-23 三菱瓦斯化学株式会社 Multilayer composite fiber
WO2010075248A1 (en) * 2008-12-23 2010-07-01 3M Innovative Properties Company Curable fiber and compositions comprising the same; method of trating a subterranean formation
FR2991330B1 (en) * 2012-06-04 2015-04-03 Arkema France COMPOSITE MATERIAL WITH VERY LOW CARBON NANOCHARGES RATES, PREPARATION METHOD AND USES THEREOF

Also Published As

Publication number Publication date
KR20170129156A (en) 2017-11-24
US11767423B2 (en) 2023-09-26
US20180080149A1 (en) 2018-03-22
US20200002853A1 (en) 2020-01-02
TW201638412A (en) 2016-11-01
CN107407010B (en) 2020-10-20
JPWO2016147998A1 (en) 2017-12-28
EP3272917A4 (en) 2018-10-24
TWI704259B (en) 2020-09-11
KR102551954B1 (en) 2023-07-05
EP3272917A1 (en) 2018-01-24
WO2016147998A1 (en) 2016-09-22
CN107407010A (en) 2017-11-28

Similar Documents

Publication Publication Date Title
JP6787309B2 (en) Antibacterial fiber
CN110774693A (en) Antibacterial and antimicrobial SMMS composite non-woven fabric
TW200844282A (en) Conjugate fibers excellent in antistatic property, water absorption and cool feeling by contact
CN107385541A (en) Application of the PHBV materials as new type natural antiseptic in textile preparation
JP2008542486A5 (en)
US20100318012A1 (en) Bacteriostatic textile based on polyamide 11
JP6806067B2 (en) Fibers for cool contact and textile products using them
US10538863B2 (en) Cloth having excellent contact cold sensation and colorfastness
JP2009507109A (en) Compositions for the production of polyester and polyamide yarns with improved moisture management properties
JP5116984B2 (en) Nonwoven fabric and method for producing the same
US20070112110A1 (en) Composition for producing polyester and polyamide yarns with improved moisture management properties
JP3010205B2 (en) Polyolefin-based synthetic fibers having antistatic and antifouling properties and molded articles thereof
KR101957439B1 (en) Material comprising 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene for multifunctional fiber, and multifunctional fiber and master batch comprising the same
KR970011932B1 (en) Method of manufacturing polypropylene nonwoven of fabrics
JP2022178824A (en) antibacterial fabric

Legal Events

Date Code Title Description
A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A821

Effective date: 20170406

A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20190110

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20191023

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20191219

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20200526

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20200630

A911 Transfer to examiner for re-examination before appeal (zenchi)

Free format text: JAPANESE INTERMEDIATE CODE: A911

Effective date: 20200708

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20200929

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20201012

R151 Written notification of patent or utility model registration

Ref document number: 6787309

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R151